Perfluoroalkyl sulfide sulfone polysulfone and polysulfide diols

ABSTRACT

Bisperfluoroalkyl-substituted diols containing sulfide, sulfone or polysulfide linkages and a method for making them are described. These diols can react with isocyanates to form urethanes; diisocyanates to form polyurethanes; chloroformates to form carbonates; with carboxylic, sulfuric or phosphoric acids or derivatives to form carboxylate esters, sulfate esters, phosphate esters respectively. These diol compounds and their derivatives are useful for imparting oil and water repellency to substrates such as glass, wood, paper, leather, wool, cotton, polyester and other substrates.

This application is a continuation of application Ser. No. 08/270,067,filed Jul. 1, 1994, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to bisperfluoroalkyldiols and their derivativeswhich impart oil water repellency on materials such as glass, wood,paper, leather, wool, cotton, polyester and other substrates.

Perfluoroalkyl-substituted polymers possess free surface energies evenlower than that of poly-tetrafluoroethylene (Teflon). They havetherefore long been used to impart oil- and water repellency to a widevariety of substrates, especially textiles. Phosphate esters ofperfluoroalkyl-substituted alcohols are also being used as oil- andwater repellent paper sizes, for instance in paper plates and in foodpackaging products. In these applications it is especially importantthat the paper sizing compound contain at least two perfluoroalkyl orR_(F) groups. When mono-R_(F) alcohols are used to esterify phosphoricacid, only the diesters are active oil- and water repellents. Themonoester is too water soluble and, even if retained on the cellulosefiber, reduces water repellency, and the triester is not substantive.However making phosphate diesters in high yield is very difficult inpractice; substantial amounts of mono- and triesters are always producedas by products. It is also impossible to prepare oil- andwater-repellent paper sizes in form of sulfuric acid half-esters frommono-R_(F) alcohols, since such esters are very water soluble anionicsurfactants and have a detrimental effect on water repellency.Mono-R_(F) -substituted alcohols and diols, though suitable for thepreparation of acrylic and methacrylic oil- and water-repellent R_(F)-polymers, are therefore less suitable for the preparation ofoil-repellent phosphate or sulfate ester acidic paper sizes.

The use of di-R_(F) -substituted alcohols and diols makes it possible toprepare highly oil-repellent phosphate or sulfate monoester paper sizes,since even a mono-ester contains two R_(F) groups. This approach andsome such compounds are described in U.S. Pat. Nos. 5,091,550 and5,132,445.

For the preparation of oil- and water-repellent polyurethanes it isespecially important that the diol contain more than one R_(F) group.Common such diols and polyurethanes thereof are described in U.S. Pat.Nos. 3,935,277; 3,968,066; 4,046,944; 4,054,592; 4,098,742; 4,946,992and 5,200,493.

Although the di-R_(F) -substituted phosphates and R_(F) -substitutedpolyurethanes described in the above patents show excellent performance,the synthesis of the bisperfluoroalkyl-substituted diols involve manysteps and costly intermediates such as R_(F) -ethylenethiols andhalogenated alcohols and diols. Copending application No. 08/270,068describes bis-perfluoroalkyl-substituted diols produced by a morestraightforward synthesis route, namely by direct addition ofperfluoroalkyl iodides (R_(F) I) to diallyl diols, followed byelimination of HI with a base. Another synthetic route to di-R_(F)-diols is described in J. Fluorine Chemistry, 62, (1993), p. 161-171. Itinvolves the dimerization of R_(F) I/allyl acetate adducts with zinc.The yields are less than 60% and numerous by-products are formed.

It has now been discovered that bisperfluoroalkyl-substituted diols canbe synthesized in high yield and purity by reaction of an R_(F)-substituted epoxide with sulfide ions in the presence of a base. Thesenovel diols, containing sulfide, polysulfide, sulfone, polysulfone anddi-thioether moieties, have not been previously reported. They areuseful for synthesizing perfluoroalkyl-substituted urethanes,polyurethanes, carboxylate esters and acids, polyesters, sulfate estersand acids, phosphate esters and acids, and carbonate esters and acids.These compounds are isolated in high yield and purity.

Some dicarboxylic acids, their metal salts and lower alkyl esters whichcontain two polyfluoroalkoxyalkyl carboxy moieties joined by --S-- or a--S-alkylene-S-- crosslink have been reported in U.S. Pat. No.3,828,098. Also, certain structures of the type R_(F) --S_(x) --R'_(F)have been reported in U.S. Pat. No. 3,700,646, where R_(F) and R'_(F)are polyfluoroisoalkoxyalkyl radicals and x is 1 to 8. Such materialswould be difficult to derivatize without significant functional grouptransformations.

DETAILED DISCLOSURE

The new bisperfluoroalkyldiols are of the formula I ##STR1## wherein R₁is a direct bond, a branched or linear alkylene of up to 6 carbon atoms,alkyleneoxyalkylene of up to 6 carbon atoms, alkylenethioalkylene of upto 6 carbon atoms, alkyleneoxy of up to 6 carbon atoms,alkenyleneoxyalkylene of up to 6 carbon atoms,alkylenethioalkyleneoxyalkylene of up to 9 carbon atoms,carbonamidoalkylene where the alkylene moiety contains up to 6 carbonatoms and the amido nitrogen is unsubstituted or further substituted bylower alkyl, sulfonamidoalklyene wherein the alkylene moiety contains upto 6 carbon atoms and the amido nitrogen is unsubstituted or furthersubstituted by lower alkyl; carbonamidoalkylenethioalkylene wherein thecarbonamidoalkylene moiety is as defined hereinabove and thethioalkylene moiety contains up to 6 carbon atoms, orsulfonamidoalkylenethioalkylene wherein the sulfonamidoalkylene moietyis as defined hereinabove and the thioalkylene moiety contains up to 6carbon atoms,

R_(x), R_(y) and R_(z) are independently of each other alkyl groups with1-5 carbon atoms or hydrogen,

h is 1 or2,

g is 0, 1, or 2, with the proviso that when h is 2, g is 0,

d is 0or 1,

D is an alkylene group with 2 to 10 carbon atoms, a dialkylene ethergroup with 4 to 10 carbon atoms, or pentaerythritol diacetate ordipropionate, and

R_(F) is a monovalent, perfluorinated, alkyl or alkenyl, straight,branched or cyclic organic radical having 3 to 20 fully fluorinatedcarbon atoms, which radical can be interrupted by one or more divalentoxygen or sulfur atoms, and each R_(F) radical is the same or different.

By lower alkyl is meant C₁ -C₅ alkyl.

Preferred are compounds wherein R₁ is a direct bond, --CH₂ --, --CH₂ CH₂--O--CH₂ --, --CH(CH₃)--, --CH₂ CH₂ --S--CH₂ --, --CH═CHCH₂ --O--CH₂ --,--SO₂ NR_(o) --CH₂ -- or --CONH--CH₂ CH₂ --O--CH₂ --, wherein R_(o) ishydrogen or an alkyl group with 1 to 4 carbon atoms, R_(x) is methyl orhydrogen, R_(y) and R_(z) are hydrogen, h is 1, g and d are zero and theR_(F) group is saturated, contains 6-18 carbon atoms, is fullyfluorinated and contains at least one terminal perfluoromethyl group.

Also preferred are compounds wherein R₁ is a direct bond, --CH₂ --,--CH₂ CH₂ --O--CH₂ --, --CH₂ CH₂ --S--CH₂ --, --CH═CHCH₂ --O--CH₂ --,--SO₂ NR_(o) --CH₂ -- or --CONH--CH₂ --O--CH₂ --, R_(x) is methyl orhydrogen, R_(y) and R_(z) are hydrogen, h is 1, g is 2, d is zero, andthe R_(F) group is saturated, contains 4-18 carbon atoms, is fullyfluorinated and contains at least one terminal perfluoromethyl group.

Also preferred are compounds wherein R₁ is a direct bond, --CH₂ --,--CH₂ CH₂ --O--CH₂ --, --CH₂ CH₂ --S--CH₂ --, --CH═CHCH₂ --O--CH₂ --,--SO₂ NR_(o) --CH₂ -- or--CONH--CH₂ CH₂ --O--CH₂ --, R_(x) is methyl orhydrogen, R_(y) and R_(z) are hydrogen, h and d are 1, g is zero, D is--CH₂ CH₂ --O--CH₂ CH₂ -- or pentaerythritol diacetate or dipropionateand the R_(F) group is saturated, contains 4-18 carbon atoms, is fullyfluorinated and contains at least one terminal perfluoromethyl group.

Most preferably, R₁ is --CH₂ --, R_(x) , R_(y) and R_(z) are hydrogen, his 1, g and d are zero and R_(F) is a fully fluorinated, linearperfluoroalkyl group with 4 to 14 carbon atoms.

It is understood that the R_(F) group usually represents a homologousmixture of perfluoroalkyl moieties. That is, an R_(F) group indicated ascontaining a certain number of carbon atoms will also contain a smallfraction of perfluoroalkyl groups with fewer carbon atoms and a smallfraction of perfluoroalkyl groups with a higher number of carbon atoms.Ordinarily, the perfluoroalkyl group preferably contains a mixture of C₄F₉ --, C₆ F₁₃ --, C₈ F₁₇ --, C₁₀ F₂₁ --, C₁₂ F₂₅ --and C₁₄ F₂₉ --radicals.

The novel diols of this invention where g is 0 are made by reaction ofan R_(F) --R₁ -substituted epoxide with Na₂ S or NaHS, resulting inthioether diols, with elemental sulfur, Na₂ S₄ or Na₂ S₅ to formpolysulfide diols, or with an organic dithiol to form di-thioetherdiols. Sulfoxides and sulfones (g is 1 or 2) can be prepared byoxidizing the corresponding thioethers with, for example, 1 or 2equivalents of an oxidizing agent, preferably a peroxide, per sulfidelinkage.

The diol-forming reaction is advantageously carried out in the presenceof water and an organic diluent or solvent. Said organic diluent orsolvent should be low boiling enough to be recoverable by distillation,including vacuum distillation, if desired. Typical useful diluents andsolvents are ketones, such as methyl propyl ketone, methyl ethyl ketoneor acetone; esters such as ethyl acetate or isopropyl acetate, andalcohols such as ethanol, n-propanol, isopropanol, n-, sec.- ortert.-butanol or allyl alcohol. Typical reaction temperatures are 40° to80° C. and reaction times are 1 to 8 hours.

Typical R_(F) -epoxides are of the formula R_(F) --R₁ --EP, wherein EPdenotes an epoxy group, --CH(--O--)CH₂, and R_(F) and R₁ are defined asabove. Said compounds are known per se or can be prepared by knownmethods. For example some such epoxides are described in U.S. Pat. Nos.4,038,195; 4,435,330; 4,490,304 and 4,577,036.

Preferred are epoxides of the formulae R_(F) --EP; R_(F) CH₂ --EP; R_(F)--CH₂ CH₂ --S--CH₂ --EP; R_(F) --CH₂ CH₂ --O--CH₂ --EP, R_(F) --CH═CHCH₂--O--CH₂ --EP, R_(F) SO₂ NR_(o) CH₂ --EP, R_(F) CONH--CH₂ CH₂ --O--CH₂--EP, with R_(F) --CH₂ --EP being the most preferred.

It has been unexpectedly found that, instead of making the noveldi-R_(F) -diols from epoxides, the halohydrin precursors of the formula

    R.sub.f --CHR.sub.v --CR.sub.x (hal)--CR.sub.y R.sub.z OH

can be used, wherein R_(v), R_(x), R_(y) , and R_(z) are hydrogen or C₁--C₅ alkyl, and hal is bromide or iodide, preferably iodide. Thesynthesis of diols of the formula Ia ##STR2## wherein R_(F), R_(v),R_(x), R_(y), R_(z), h and d are as defined above, by reaction of

    R.sub.F --CHR.sub.v --CR.sub.x (hal)CR.sub.y R.sub.z --OH,

wherein hal is bromide or iodide, with Na₂ S, Na₂ S₄ or an organicdithiol of the formula HS-D-SH, wherein D is defined as above, in abasic aqueous medium, is thus another embodiment of this invention.Suitable bases for the basic aqueous medium are alkali metal hydroxidessuch as sodium and potassium hydroxide.

In the preferred halohydrins, R_(v) and R_(x) are hydrogen or methyl,R_(y) and R_(z) are hydrogen and hal is iodine, with R_(v) and R_(x)also as hydrogen being most preferred.

The most preferred di-R_(F) R₁ -diol isheptane-1,7-di-perfluoroalkyl-4-thia-2,6-diol. It can be prepared in onereactor by 1) addition of an R_(F) -iodide to allyl alcohol to form theiodohydrin, followed by 2) reaction of the iodohydrin with a sulfide.The epoxide of the formula R_(F) --CH₂ --EP is formed in lowconcentrations as an intermediate during the second step, but does notaccumulate as an isolatable compound and is not present in the reactionproduct. The process of making the preferred diols by reaction of 2moles of a 2-iodo-3-perfluoroalkyl-1-propanol with one mole of a sulfideis another embodiment of this invention.

The addition of an R_(F) -iodide to allyl alcohol to give an iodohydrinintermediate proceeds readily in the presence of a free radicalinitiator such an azo compound or a peroxide at conventional initiationtemperatures of 35° to 150° C. It was found, however, that only in thepresence of small amounts of aqueous solutions of sulfite, bisulfite ordithionite ions does the reaction proceed fast enough and areconversions high enough to make the synthesis commercially practical.This novel process to make the R_(F) -iodide-allyl alcohol iodohydrinintermediate and other related compounds is described separately incopending application No. 08/270,068.

Solvents can be present during this step; for example ketones such asacetone, methyl ethyl ketone or methyl propyl ketone, esters such asisopropyl acetate, alcohols such as ethanol or butanol, ethers such asdioxane or di-(2-hydroxyethyl)-ether, hydrocarbons such as toluene oroctane, amides such as dimethylformamide and lactams such asN-methylpyrrolidone.

In the second step the iodohydrin intermediate, a2-iodo-3-perfluoroalkyl-1-propanol, is reacted with Na₂ Sx9H₂ O in thepresence of water and an organic diluent or solvent to give aheptane-1,7-di-perfluoroalkyl-4-thia-2,6-diol. Typical diluents andsolvents are ketones, such as methyl propyl ketone, methyl ethyl ketoneor acetone; esters such as ethyl acetate or isopropyl acetate; alcoholssuch as ethanol, n-propanol, isopropanol, n-, sec.- or tert. butanol orallyl alcohol. Preferably the same solvent is used as for the previousstep. Typical reaction temperatures are 40° to 80° C. and reaction timesare 1 to 8 hours.

The key step is the in-situ preparation of a3-perfluoroalkyl-1,2-epoxypropane as a transitory, non-isolatableintermediate. Evidence of a 3-perfluoroalkyl-1,2-epoxypropane being anintermediate is shown in Example 2. In said example, a3-perfluoroalkyl-1,2-epoxypropane is converted toheptane-1,7-di-perfluoroalkyl-4-thia-2,6-diol using Na₂ Sx9H₂ O. Thesame novel diols can also be prepared by the addition of NaHS to a2-iodo-3-perfluoroalkyl-1-propanol.

Instead of allyl alcohol, methallyl alcohol or crotyl alcohol can beused to prepare analogous diols of the formula Ia.

Disulfides and polysulfides of formula (I) can be prepared from thereaction of Na₂ S plus elemental sulfur or just elemental sulfur with anR_(F) -iodide at elevated temperatures. Na₂ S₄ and/or Na₂ S₅ may also beutilized. These reagents will give a mixture of sulfide and polysulfidestructures of formula I, ranging from 1 to 4 sulfur atoms in the crosslinkage.

The sulfides and polysulfides of formula I may be oxidized to thecorresponding sulfoxides and polysulfoxides or to sulfones andpolysulfones. This functional group transformation may be accomplishedby the addition of one equivalent of an oxidizing agent, preferably aperoxide, per sulfide linkage or two or more equivalents to give,respectively, sulfoxide/polysulfoxide or surfone/polysulfone structuresof formula I.

Di-thioether diols of formula I can be prepared by reaction of a2-iodo-3-perfluoroalkyl-1-propanol or an R_(F) -substituted epoxide witha dithiol, for example dimercaptoethylene or pentaerythritoldimercaptopropionate.

The diols of formula I can be further reacted with isocyanates to formurethanes; diisocyanates to form polyurethanes; with carboxylic,sulfuric or phosphoric acids or derivatives to form carboxylate esters,sulfate esters, phosphate esters, or carbonates, respectively. Use ofthese reaction products and their further derivatives impart oil andwater repellency to materials such as glass, wood, paper, leather,textiles such as wool, cotton, polyester and other substrates is anotherobject of this invention.

Useful esters are mono- and diesters of the formula IIa or IIb ##STR3##wherein R_(F), R₁, R_(x), D, and d are defined as above, T is hydrogenor R₂ --CO--, where R₂ is C₁ -C₂₀ alkyl, C₆ -C₁₄ aryl or C₇ -C₁₆aralkyl, each of which is unsubstituted or substituted by one or morehydroxy, thiol, carboxyl or C₁ -C₄ alkyl ester groups and W is hydrogenor HOOC--R₃ --CO--, where R₃ is a direct bond, an alkylene of 1-16carbon atoms, an arylene of 6 to 14 carbon atoms or an alkarylene of 7to 16 carbon atoms, which alkylene, arylene or alkarylene isunsubstituted or substituted by C₁ -C₄ alkyl, chlorine or bromine.

Structurally, R₂ is the radical residue of a carboxylic acid of theformula R₂ --COOH. Typical examples of R₂ --COOH include acetic,benzoic, hydroxybenzoic, acrylic, methacrylic, thioacetic andthiopropionic acids and the C₁ -C₄ alkyl monoesters of terephthalic,phthalic, citric, maleic, fumaric, itaconic, malonic, succinic andthiosuccinic acids.

Preferred esters of the formula IIa are those wherein R₁ is a directbond, --CH₂ --, --CH(CH₃)--, --CH₂ CH₂ --O--CH₂ --, --CH₂ CH₂ --S--CH₂--, --CH═CHCH₂ --O--CH₂ --, --SO₂ NR_(o) --CH₂ -- or --CONH--CH₂ CH₂--O--CH₂ --, wherein R_(o) is hydrogen or an alkyl group with 1 to 4carbon atoms, R_(x) is hydrogen or methyl, d is zero, R₂ --CO-- is theradical of acetic, benzoic, hydroxybenzoic, acrylic, methacrylic,thio-acetic or thio-propionic acid, or a C₁ -C₄ alkyl monoester ofterephthalic, phthalic, citric, maleic, fumaric, itaconic, malonic,succinic or thiosuccinic acid and R_(F) is saturated, contains 6-18carbon atoms, is fully fluorinated and contains at least one terminalperfluoromethyl group. Of these, monomaleates and monosuccinates andmono-ortho- and terephthalates of the formula IIa, especially thosewherein R₁ is --CH₂ and R_(x) is hydrogen are especially preferred.

Structurally, R₃ is the divaient radical residue of a dicarboxylic acidof the formula HOOC--R₃ --COOH. Such dicarboxylic acids include oxalic,maleic, fumaric, malonic, succinic, glutaric, itaconic, adipic, pimelic,suberic, azelaic, sebacic, brassylic, octadecanedioic, dimer acid,1,4-cyclohexanedicarboxylic, 4,4'-dicyclohexyl-1,1'-dicarboxylic,phthalic, isophthalic, terephthalic, methylphthalic, chlorophthalic,diphenyl-2,2'-dicarboxylic, diphenyl-4,4'dicarboxylic, 1,4-naphthalenedicarboxylic, diphenylmethane-2,2'-dicarboxylic,diphenylmethane-3,3'-dicarboxylic, diphenylmethane-4,4'-dicarboxylicacid and the like. Also included are compounds wherein R₃ is substitutedby one or two carboxy groups and is derived, for example, fromtrimellitic anhydride, pyromellitic dianhydride or benzophenonetetracarboxylic acid dianhydride. Compounds of the formula IIb whereinR₃ is the divalent radical residue of maleic, succinic or adipic acidare preferred.

Also useful are polyesters containing units of the formula 11c ##STR4##wherein R_(F), R_(x), R₁, R₃, D, and d are defined as above.

Preferably the polyesters of the formula IIc have molecular weights fromabout 3,000 to 30,000.

Preferred esters of the formulae IIb and IIc are those wherein R₁ is adirect bond, --CH₂ --, --CH(CH₃)--, --CH₂ CH₂ --O--CH₂ --, --CH₂ CH₂--S--CH₂ --, --CH═CHCH₂ --O--CH₂ --, --SO₂ NR_(o) --CH₂ -- or--CONH--CH₂ CH₂ --O--CH₂, wherein R_(O) is hydrogen or an alkyl groupwith 1 to 4 carbon atoms, R_(x) is hydrogen or methyl, d is zero, andR_(F) is saturated, contains 6-18 carbon atoms, is fully fluorinated andcontains at least one terminal perfluoromethyl group. Of these, esterswherein R₁ is --CH₂ --, R_(x) is hydrogen, --OOC--R₃ --COO-- is thediradical of maleic, succinic, or adipic acid and R_(F) is a fullyfluorinated, linear perfluoroalkyl group with 4 to 14 carbon atoms areespecially preferred.

Also useful are carbonates derived from a bischloroformate, e.g.ethylene glycol bischloroformate.

Useful phosphates are of the formula III ##STR5## wherein Q is ##STR6##b is one or zero, M and M₁ are hydrogen, ammonium, C₁ --C₅ alkyl- or C₁--C₅ hydroxyalkyl-substituted ammonium or an alkali metal cation, andR_(F), R₁, R_(x), D, g and d are defined as above, with the proviso thatwhen b is zero, M₁ is hydrogen.

Preferred are phosphates wherein R₁ is a direct bond, --CH₂ --,--CH(CH₃)--, --CH₂ CH₂ --O--CH₂ --, --CH₂ CH₂ --S--CH₂ --, --CH═CHCH₂--O--CH₂ --, --SO₂ NR_(o) --CH₂ -- or --CONH--CH₂ CH₂ --O--CH₂ --,wherein R_(o) is hydrogen or an alkyl group with 1 to 4 carbon atoms, dis zero, R_(x) is hydrogen or methyl and R_(F) is saturated, contains6-18 carbon atoms, is fully fluorinated and contains at least oneterminal perfluoromethyl group. Especially preferred are phosphateswherein R₁ is --CH₂ --, R_(x) is hydrogen and R_(F) is a fullyfluorinated, linear perfluoroalkyl group with 4 to 14 carbon atoms.

Useful sulfates are of the formula IV ##STR7## wherein one of f and k iszero and the other is 1, and M, R_(F), R₁, R_(x) d and D are defined asabove.

Preferred are sulfates wherein R₁ is a direct bond, --CH₂ --,--CH(CH₃)--, --CH₂ CH₂ --O--CH₂ --, --CH₂ CH₂ --S--CH₂ --, --CH═CHCH₂--O--CH₂ --, --SO₂ NR_(o) --CH₂ -- or --CONH--CH₂ CH₂ --O--CH₂ --,wherein R_(o) is hydrogen or an alkyl group with 1 to 4 carbon atoms, kis 1, d and f are zero, D is --CH₂ CH₂ --O--CH₂ CH₂ -- orpentaerythritol diacetate or dipropionate, R_(x) is hydrogen or methyland the R_(F) group is saturated, contains 4-18 carbon atoms, is fullyfluorinated and contains at least one terminal perfluoromethyl group.Especially preferred are sulfates wherein R₁ is --CH₂ --, R_(x) ishydrogen, d and f are zero and R_(F) is a fully fluorinated, linearperfluoroalkyl group with 4 to 14 carbon atoms.

Useful urethanes are the reaction products of a diol of the formula Iwith an isocyanate of the formula R₄ --NCO, wherein R₄ is the monovalenthydrocarbon radical of phenyl isocyanate, m-isopropenyl-methyl benzylisocyanate (TMI), 2-isocyanatoethyl acrylate or methacrylate (IEM) or1,1-dimethyl-2-isocyanatoethyl-m-isopropenylphenyl.

Useful polyurethanes consist of or contain repeating units of thegeneral formula V ##STR8## wherein R_(F), R₁, R_(x), D and d are definedas above, and R₅ is the diradical residue of a diisocyanate of theformula OCN--R₅ --NCO.

Preferred polyurethanes are those wherein R₁ is a direct bond, --CH₂ --,--CH(CH₃)--, --CH₂ CH₂ --O--CH₂, --CH₂ CH₂ --S--CH₂ --, --CH═CHCH₂--O--CH₂ --, --SO₂ NR_(o) --CH₂ -- or --CONH--CH₂ CH₂ --O--CH₂ --,wherein R_(o) is hydrogen or an alkyl group with 1 to 4 carbon atoms,R_(x) is hydrogen or methyl and d is zero, and the R_(F), group issaturated, contains 4-18 carbon atoms, is fully fluorinated and containsat least one terminal perfluoromethyl group and the group R₅ isaromatic, aliphatic or cycloaliphatic.

Useful aromatic diisocyanates include toluene diisocyanate (TDI) (allisomers), 4,4'-diphenylmethane diisocyanate (MDI), tolidinediisocyanate, dianisidine diisocyanate, m-xylylene diisocyanate,p-phenylene diisocyanate, m-phenylene diisocyanate,1-chloro-2,4-phenylene diisocyanate, 3,3'-dimethyl-4,4'-bisphenylenediisocyanate,4,4'-bis(2-methyl-isocyanatophenyl)methane-4,4'-bisphenylenediisocyanate, 4,4'-bis(2-methoxyisocyanatophenyl)methane,1-nitrophenyl-3,5-diisocyanate, 4,4'-diisocyanatodiphenyl ether,3,3'-dichloro-4,4'-diisocyanatodiphenyl ether,3,3'-dichloro-4,4'-diisocyanatodiphenylmethane,4,4'-diisocyanatodibenzyl, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl,2,2'-dimethyl-4,4'-diisocyanatodiphenyl,2,2'-dichloro-5,5'-dimethoxy-4,4'-diisocyanatodiphenyl,3,3'-dichloro-4,4'-diisocyanatodiphenyl, 1,2-naphthalene diisocyanate,4chloro-1,2-naphthalene diisocyanate, 4-methyl-1,2-naphthalenediisocyanate, 1,5-naphthalene diisocyanate, 1,6-naphthalenediisocyanate, 1,7-naphthalene diisocyanate, 1,8-naphthalenediisocyanate, 4-chloro-1,8-naphthalene diisocyanate, 2,3-naphthalenediisocyanate, 2,7-naphthalene diisocyanate, 1,8-dinitro-2,7-naphthalenediisocyanate, 1-methyl-2,4-naphthalene diisocyanate,1-methyl-5,7-naphthalene diisocyanate, 6-methyl1,3-naphthalenediisocyanate and 7-methyl-1,3-naphthaiene diisocyanate.

Useful aliphatic or cycloaliphatic polyisocyanates include 1,2-ethanediisocyanate, propylene-1,2- and -1,3 diisocyanate, 1,4-tetramethylenediisocyanate, 2-chloropropane1,3-diisocyanate, pentamethylenediisocyanate, 1,8-octane diisocyanate, 1,10-decane diisocyanate,1,12-dodecane, 1,16-hexadecane diisocyanate and other aliphaticdiisocyanates such as 1,3-cyclohexane diisocyanate and 1,4-cyclohexanediisocyanate.

Additionally, the following diisocyanates are particularly preferredbecause urethane compositions made therefrom tend to be non-yellowing:1,6-hexamethylene diisocyanate (HDI), 2,2,4- and2,4,4-trirnethyl-1,6-diisocyanatohexane (TMDI), dimer acid-deriveddiisocyanate (DDI), obtained from dimerized fatty acids such as linoleicacid, 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI),isophorone diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyldiisocyanate, lysine methyl ester diisocyanate (LDIM),bis(2-isocyanatoethyl) fumarate (FDI), bis(2-isocyanatoethyl) carbonateand m-tetramethylxylylene diisocyanate (TMXDI).

Especially preferred are polyurethanes wherein R₁ is --CH₂ --, R_(x) ishydrogen, d is zero, and R_(F) is saturated and contains 6-18 carbonatoms, is fully fluormated and contains at least one terminalperfluoromethyl group, and R₅ is the diradical residue of isophoronediisocyanate, 2,2,4(2,4,4)-trimethyl-1,6-diisocyanatohexane, linoleicdimer acid-derived diisocyanate, 1,6-hexamethylene diisocyanate or3-isocyanatomethyl-3,5,5-trimethylcyclohexyl diisocyanate.

It is preferred that the polyurethanes have molecular weights from about3,000 to 30,000.

Esters of the formulae IIa-IIc and carbonates may be prepared byreacting diols of formula I with acid chlorides, esters orchloroformates to yield carboxylate esters and carbonates respectively.For example, acetyl chloride can be reacted with a diol of formula I togive an acetate derivative. This reaction is preferably carried out inthe presence of an organic amine to scavenge HCl.

Sulfate esters are prepared by the reaction of the inventive diols withchlorosulfonic acid or, preferably, with sulfamic acid in the presenceof a base or a basic solvent such as pyridine, N-methylpyrrolidone, ureaor tetramethylurea. This reaction is usually carried out at about100°-105° C. for 2 to 10 hours. The advantage of using sulfamic acidrather than chlorosulfonic acid is the direct formation of an ammoniumsalt in a single step.

The reaction of a diol of formula I with polyphosphoric acid or POCl₁₃will give a phosphate ester of the formula III. This reaction istypically carried out at about 85° C. using glyme as solvent. Thesephosphates are usually reacted with a base such as ammonia to convertthem to the corresponding ammonium salts for water solubility and forapplication testing.

Polyurethanes are prepared from the diols of this invention by the knownmethods of polyurethane chemistry. These polyurethanes may also containother building blocks derived from commercially available diols ordiamines, especially tertiary amino group-containing diols such asN-methyldiethanolamine, polyethylene oxide diols and3-aminopropyl-terminated polyethylene oxide (Jeffamine-ED, from TEXACOCorp.), poly-(dimethylsiloxane)-dialkanols andpoly-(dimethylsiloxane)-dialkylamino. Typical polyurethane compositionsincorporating known diols and diamines in combination with certain otherperfluoroalkyl-substituted diols are described for example in U.S. Pat.Nos. 3,968,066, 4,046,944 and 4,098,742.

Also, this invention relates to a substrate containing 0.01 to 10% byweight of a fluorine-containing composition, at least part of saidfluorine being provided by one or more compounds derived from an R_(F)-diol of formula I. Such subsnantes include glass, wood, paper, leather,textiles such as nylon, wool, cotton, polyester, and other substrates.The above reaction products and their further derivatives of the diolsof formula I impart oil and water repellency to said substrates. Saidsubstrates and methods of preparing them are further objects of thisinvention.

The following examples are intended for illustrative purposes only, andare not intended to restrict the scope of the invention in any way.

Example 1

Synthesis of a 2-iodo-3-perfluoroalkyl- 1-propanol.

Into a 1 l round-bottomed-flask equipped with condenser, thermometer,stirrer and a nitrogen gas inlet tube are charged 606.0 g (1.0 mole) ofa perfluoroalkyl iodide (R_(F) I) with a homologue distribution of 1.7%C₆, 49.8% C₈, 33.5% C₁₀, 11.1% C₁₂, 3.1% C₁₄, 0.69% C₁₆ and0.16% C₁₈,(Telomer-AN, from DuPont), 22.6 g H₂ O (1.26 mole) and 14.8 g sodiummetabisulfite (Na₂ S₂ O₅ 0.078 mole). The mixture is heated on an oilbath to 80° C. with stirring. After the addition of 2.88 g (0.015 mole)2,2'-azo-bis-(2-methylbutyronitrile) (VAZO-67, from WAKO Chem. Co.),112.8 g allyl alcohol (1.16 mole) as a 60% solution in water arecontinuously added over 210 minutes using a Masterflex pump at a flowrate of 32.2 g/h. A small temperature increase of the reaction mass isobserved. Product formation was followed by monitoring the decrease ofR_(F) I concentration via gas chromatography. No substantialaccumulation of R_(F) I is seen, i.e. the allyl alcohol reactsimmediately upon addition.

After 210 minutes, the addition rate of the aqueous allyl alcoholsolution is increased to 102 g/h for the following two hours. The totalamount of allyl alcohol solution used in the reaction is 318.2 g,corresponding to a molar ratio of R_(F) I to allyl alcohol=1.0:3.28. Thetotal amount of water used is 31.5%, based on R_(F) I.

The formed 2-iodo-3-perfluoroalkyl-1-propanol is obtained as a solutionin the excess of aqueous allyl alcohol. The excess allyl alcohol isdistilled oil in vacuo and the product is filtered oil, rinsed withdeionized water and dried in vacuo at 50° C. It is obtained as adark-yellow waxy solid in 98% yield; the conversion of R_(F) I is 100%.

Example 2

Heptane- 1,7 -di-perfluoroalkyl-4-thia-2,6-diol.

Into a 300 ml, three neck round-bottomed flask are placed the2-iodo-3-perfluoroalkyl-1propanol of Example 1 (70 g, 0.105 mol), 26 gwater, 17 g ethanol and 8.6 g methyl propyl ketone (MPK). The mixture isstirred at 42° C. and solid Na₂ Sx9H₂ O (126 g, 0.053 mol) is added overa 30 minute period. After the addition is completed, the reactionmixture is heated to 55° C. The progress of the reaction is monitored bygas chromatography. After one hour the reaction is complete. The MPK isdistilled oil at 80° C., whereupon the mixture separates into twophases. The aqueous phase is removed and the organic phase is washedtwice with 10% HCl. Small amounts of residual MPK are removed undervacuum. A light yellow crystalline material is obtained and dried invacuum (45° C.) to give 110 g (95% yield) of the title di-R_(f) -diolwith a melting point, m.p., of 118° C.

The structure is confroned by H-NMR (CDCl₃, 500 MHz): d 4.3 (2H, bs,--CHOH), 2.7 and 2.9 (4H, m, --CH₂ S--) and 2.4 (4H, m, R_(F) CH₂).

Example 3

Heptane-1,7-di-perfluoroalkyl-4-thia-2,6-diol; preparation from aperfluoroalkyl-propylene oxide.

Into a 2 l three-neck round-bottomed flask equipped with a mechanicalstirrer are poured melted C₉ --C₂₁ -perfluoroalkyl-propylene oxide(ZONYL-TE; DuPont Chem. Corp.) (559.0 g, 0.98 mol) and 38 ml acetone.This mixture is stirred at 43° C. until it turns clear. To this mixtureis added a solution of Na₂ Sx9H₂ O (120.1 g, 0.49 mol) in 135 ml waterover a 50 minute period. During the addition the temperature of thereaction mixture is maintained at about 43° C. by using a cooling bath.After the addition of Na₂ Sx9H₂ O is complete, the stirred yellow turbidmixture is heated at 55° C. for 2 hours. The progress of the reaction ismonitored by gas chromatography. After 2 hours the reaction is complete.Acetone is removed from the reaction mixture by distillation at 78° C.and the remaining aqueous slurry is filtered. The filter cake is washedthree times with 200 ml of cold water. Subsequent drying of the filtercake under vacuum gives 555.0 g (96.5% yield) of a tan powder with am.p. of 118°-124° C. and a fluorine content of 63.4% (Calculated:63.2%). NMR data are identical to those obtained for Example 2.

Example 4

Synthesis of a polyurethane.

40.09 g (42.2 mmoles) of theheptane-1,7-di-perfluoroalkyl-4-thia-2,6-diol of Example 2 and 93.04 gisopropyl acetate are placed into a 250 ml 3-necked round-bottomed flaskfitted with a mechanical stirrer, gas inlet, thermometer, Dean-Starktrap and condenser. The mixture is kept under nitrogen and heated toreflux to remove water as an azeotrope with the isopropyl acetate: 20 mlof distillate are collected in the trap.

The contents are cooled to 75° C. and 6.74 g (31.6 mmoles) of2,2,4-trimethyl-1,6-diisocyanatohexane (TMDI) is added, followed by 0.10g (16 mmoles) of dibutyltin dilaurate (DBTL). The flask contents arestirred for approximately one hour at 80° C., or until the TMDI contentis below 0.2% as determined by IR.

15.62 g (26.4 mmoles) of dimer acid diisocyanate (DDI 1410, from HenkelChemie) and 1.90 g (15.9 mmoles) of N-methyl diethanolamine (NMDEA) areadded, followed by 26.2 g isopropyl acetate as a rinse. The mixture isstirred for 2 hours at 80° C. After this time no more NCO groups remainpresent as determined by IR-spectroscopy. The product polyurethane isobtained as a 40% solution in isopropyl acetate. It contains the diol,TMDI, DDI, and NMDEA in a mol ratio of 4:3:2.5:1.5. On drying, thepolyurethane forms a clear tough, highly oil- and water-repellent film.

Example 5

The following example demonstrates the usefulness of a novelpolyurethane as an oil and water-repellent textile finish.

Emulsification

In 93.8 g water are dissolved 1.87 g Arquad-2C/75(dicocodimethylammonium chloride, from Akzo Corp.) and 0.63 g Ethoquad18/25 (methyl-polyoxyethyl(15)-octadecyl ammonium chloride, from AkzoCorp.) to make up the aqueous phase. The polyurethane solution ofExample 4 is adjusted to 40% solids with isopropyl acetate, forming theorganic phase. Both solutions are heated to 60-70° C. Then 45 g of thepolyurethane solution is added to the aqueous phase while stirring. Thismixture is homogenized first with a high-shear stirrer (POLYTRON) for 2minutes, followed by 2-3 passes through a MICROFLUIDIZER at 5000-7000psi. The emulsion is then stripped free of organic solvent on a rotaryevaporator at reduced pressure.

Application

The polyurethane emulsion is formulated into a pad bath containing 6% byweight of the permanent press resin Permafresh-113B (Sequa Chem. Corp.),1.2% Catalyst 531 (Zn(NO₃)₂) and an amount of polyurethane emulsioncalculated to result in 0.12% fluorine in the bath. This mixture isapplied to cotton fabric at 85% wet pick-up. The fabric is dried for 10min. at 110° C. and cured for 5 min. at 150° C. The test results areshown in the table. They demonstrate excellent performance, even afterrepeated washing and drycleaning.

Test Methods

The AATCC Water Spray test rating was determined according to StandardTest method 22-1985 of the American Association of Textile Chemists andColorists, Volume 61, 1986 (also designated ASTM-D-583-58). Ratings aregiven from 0 (minimum) to 100 (maximum).

The AATCC Oil Rating was determined according to Standard Test method118-1983 of the American Association of Textile Chemists and Colorists.Ratings are given from 0 (minimum) to 8 (maximum). A commonly acceptedlevel of repellency for oil-repellent coatings in the United States isan oil repellency of 4.

The Bundesmann test simulates the conditions of a fabric being wornduring a heavy rain. In this test water absorption is measured inpercent pick-up, (underlined numbers in the following table) andappearance (3 samples), rated from 1 (lowest) to 5 (highest rating).

    ______________________________________                                        TEST RESULTS                                                                           Oil kit  spray      Bundesmann                                       ______________________________________                                        initial    6          3 × 100                                                                            11; 5,5,5                                    5 × 60° wash                                                                5          3 × 80                                                                             23; 2,1,1                                    1 × dryclean                                                                       4          100,90,90  27; 5,3,2                                    ______________________________________                                    

Example 6

This example illustrates the synthesis of di-perfluoroalkyl sulfateesters by reaction of a heptane-1,7-di-perfluoroalkyl-4-thia-2,6-diolwith sulfamic acid.

Into a 100 ml round-bottomed flask are placed theheptane-1,7-di-perfluoroalkyl-4-thia-2,6diol of Example 2 (19.4 g,0.0150 mol), sulfamic acid (2.62 g, 0.027 mol) and 5.0 g oftetramethylurea. This mixture is stirred under nitrogen for 1.5 hours at103° C. The progress of the reaction and the final degree of sulfationis monitored by a two-phase titration of the forming di-perfluoroalkylsulfate ammonium salt with benzethonium chloride solution according tothe procedure described in "Analysis of Surfactants", Surfactant Sci.Series, Vol. 40, (Marcel Decker Inc., New York, 1992).

The final degree of sulfation, expressed as OH equiv.sub.·initial - OHequiv.sub.·final, is 0.85.

The product is dissolved in water and used for application tests.

Example 7

The following example demonstrates the usefulness of the sulfateester-acids as oil-repellent paper sizes.

Sample Preparation and Testing

External Size Application

Samples of the product of Example 6 are diluted to the test applicationlevels with distilled water. The solutions are added to a 4% aqueoussolution of paper maker's starch (Stayco M, oxidized starch, from StaleyCorp.) and then applied to unsized paper by padding (paper dippedthrough starch solution, and passed through single nip rollers). Theresulting sheets are dried at ambient conditions for 15 minutes, then 3minutes at 200° F. in an "Emerson Speed Drier" (heated metal plate withcanvas cover).

Oil Kit Test

The oil repellency of the surface is determined by using the TAPPI UM557 OIL KIT TEST, which consists of determining which of twelve Castoroil-heptane-toluene mixtines having decreasing surface tension causespenetration to occur within 15 seconds: ratings go from 1 (lowest) to12.

Grease Resistance Test

Grease resistance is determined with the Ralston-Purina RP-2 test forpet food materials; Ralston-Purina Company, Packaging Reference ManualVolume 06--Test Methods.

In summary; cross-wise creased test papers are placed over a grid sheetimprinted with 100 squares. Five grams of sand are placed in the centerof the crease. A mixture of synthetic oil and a dye for visualization ispipetted onto the sand and the samples are maintained at 60° C. for 24hours. Ratings are determined by the percentage of stained grid segmentson at least two samples.

Internal Size Application and Testing

Six grams of dry recycled pulp consisting of≈70% hard-wood and 30%soft-wood are diluted in 289 ml distilled water and thoroughly dispersedin a blender. To this pulp slurry is added a 1% dilution (as is) of thetest dispersion in distilled water and mixed in for 5 minutes. Then 6 mlof a 1% aqueous solution of cooked cationic starch is added and mixedtogether for an additional 5 minutes. To this 24 ml of a 50% (on solids)dilution of a water-repellent adjuvant (Hercon-76, from Nalco Chem.Corp.) are added and mixed in for another 10 minutes. The resultingslurry is diluted with an additional 500 ml of distilled water and mixedagain. This mixture is then poured over a 100 mesh wire screen, with avacuum applied from below which pulls the water from the pulp mixture toform a sheet on the screen. The wet sheet is removed from the screen anddried between another screen and a hard surface at a pressure ofapproximately 0.4 lb./in² at 110° C. for 1 1/2 hours.

Hot-Oil Test

One ml of hot (110° C.) corn oil is placed on the paper and the time isnoted for penetration to occur (20 min. maximum). Paper made in the samemanner as above, including the cationic starch and water repellentadjuvant but without a fluorochemical of this invention, demonstrates anoil kit number of<1. It holds the hot corn oil for less than one minute(begins to penetrate as soon as applied).

The amount of oil absorbed is determined gravimetrically by weighing thepaper before and after the hot oil test, after the surface oil has beenremoved.

The Oil-Kit Test is the same as that for the External Size.

The test results are shown in the following table:

    ______________________________________                                                  External Internal Size                                                        Size            Hold-out                                                            oil     RP-2 oil  time   % oil                                Ex. No. 7                                                                              % F.   kit     test kit  (min.) absorbed                             ______________________________________                                        Compound 0.05   5       2 × 0                                                                        3     <3    44                                   of       0.07   7       2 × 0                                                                        4     >20   0                                    Example 6                                                                              0.10   10      2 × 0                                                                        5     >20   0                                    ______________________________________                                    

Example 8

Conversion of a sulfur diol to a sulfone.

A 100 ml single-necked, round-bottomed flask equipped with a stirringbar and cold water condenser is charged with 19.0 g (0.32 mol) glacialacetic acid and 25.0 g (0.025 mol) of the diol of Example 3. With goodstirring, the diol is dissolved by heating to 40° C. and 2.9 g (0.08mol, 34%) hydrogen peroxide is added, during which the mixture turnsdark amber. After one hour, the reaction mixture is heated to 100° C.and an additional 5.7 g (0.17 mol, 34%) hydrogen peroxide are charged.After 3 hours the product mixture is poured into 1 liter of crushed iceand water, filtered through a Buchner funnel, washed several times withcold water, and dried under vacuum to provide 25.2 g (91%) of tancrystals with a melting point of 125°-128° C.; the structure isconfirmed by NMR: (DMF-D₇, 500 MHz) d: 5.8 (2H, bs, --OH--), 4.6 (2H, m,--CH(OH)--), 3.2 (4H, m, --CH₂ SO₂ --), 2.8-2.4 (4H, m, -CF₂ CH₂ --).

Example 9

Synthesis of a disulfide diol.

The 2-iodo-3-perfluoroalkyl-1-propanol of Example 1, 13.3 g (20 mmol),in 6 g ethanol is magnetically stirred in a three-necked round-bottomedflask at 54° C. A solution of 2.4 g (90%, 12.4 mmol) sodiumtetrasulfide, 2 g ethanol and 2.3 g water are added through an additionfunnel over 30 minutes to give a thick, yellow, paste. After holding forone hour at 54° C., the temperature is raised to 75° C. and held therefor 5 hours. GC analysis at this time shows 85% conversion of the2-iodo-3-perfluoroalkyl-l-propanol. The product mixture is evaporated todryness and washed with cold, slightly acidic deionized water to give11.1 g (92%) of a gray solid. Analysis by GC/MS of the crude mixtureshows instead of the tetrasulfide the disulfide of the formula: ##STR9##

Example 10

Synthesis of a di-thioether diol.

The 2-iodo-3-perfluoroalkyl-1-propanol of Example 1 (10 g, 15 mmol) in10 g ethanol are magnetically stirred at 49° C. in a 50 ml three-necked,round-bottomed flask. To this solution is added through a droppingfunnel over 35 minutes a solution of 1.1 g (95%, 7.5 mmol)di(2-mercaptoethyl) ether, 3.0 g (50%, 1.6 mmol) sodium hydroxide and4.1 g ethanol to give an oil-white paste. Next 5.8 g acetone is addedand the solution is stirred at 49° C. for 2 hours, then refluxed at 76°C. for one hour. The product mixture is evaporated to dryness underreduced pressure at 65° C. on a rotary evaporator. The resulting cake isstirred in 500 ml of ice cold diluted HCl (pH<3), filtered through aBuchner funnel and dried under reduced pressure at 60° C. GC analysis ofthe yellow solid (8,4 g, 95%, m.p. 95°-107° C.) shows completeconversion of the 2-iodo-3-perfluoroalkyl-1-propanol to product. Thestructure of the product, ##STR10## is confirmed by GC/MS.

What is claimed is :
 1. A bis-perfluoroalkyldiol of the formula I##STR11## wherein R₁ is a direct bond, a linear or branched alkylene ofup to 6 carbon atoms, alkyleneoxyalkylene of up to 6 carbon atoms,alkylenethioalkylene of up to 6 carbon atoms, alkyleneoxy of up to 6carbon atoms, alkenyleneoxyalkylene of up to 6 carbon atoms,alkylenethioalkyleneoxyalkylene of up to 9 carbon atoms,carbonamidoalkylene where the alkylene moiety contains up to 6 carbonatoms and the amido nitrogen is unsubstituted or further substituted bylower alkyl, sulfonamidoalklyene wherein the alkylene moiety contains upto 6 carbon atoms and the amido nitrogen is unsubstituted or furthersubstituted by lower alkyl; carbonamidoalkylenethioalkylene wherein thecarbonamidoalkylene moiety is as defined hereinabove and thethioalkylene moiety contains up to 6 carbon atoms, orsulfonamidoalkylenethioalkylene wherein the sulfonamidoalkylene moietyis as defined hereinabove and the thioalkylene moiety contains up to 6carbon atoms,R_(x), R_(y) and R_(z) are independently of each otherhydrogen or an alkyl group with 1-5 carbon atoms, h is 1 or2, g is 0, 1,or 2, with the proviso that when h is 2, g is 0, d is 0 or 1, D is analkylene group with 2 to 10 carbon atoms, a dialkylene ether group with4 to 10 carbon atoms, or pentaerythritol diacetate or dipropionate, andR_(F) is a monovalent, perfluorinated, alkyl or alkenyl, linear,branched or cyclic organic radical having 3 to 20 fully fluorinatedcarbon atoms, and each R_(F) radical is the same or different, with theproviso that when R₁ is --CH₂ --, h is 1 and g and d are 0, R_(x) ismethyl or each R_(F) group is linear.
 2. A compound according to claim1, wherein R₁ is a direct bond, --CH₂ --, --CH(CH₃)--, --CH₂ CH₂--O--CH₂, --CH₂ CH₂ --S--CH₂, --CH═CHCH₂ O--CH₂ --, --SO₂ NR_(o) --CH₂-- or --CONH--CH₂ CH₂ --O--CH₂ --, wherein R_(o) is hydrogen or an alky,1 group with 1 to 4 carbon atoms, R_(x) is methyl or hydrogen, R_(y) andR_(z) are hydrogen, h is 1, g and d are zero and the R_(F) group issaturated, contains 6-18 carbon atoms, is fully fluorinated and containsat least one terminal perfluoromethyl group.
 3. A compound according toclaim 1, wherein R₁ is a direct bond, --CH₂ --, --CH(CH₃)--, --CH₂ CH₂--O--CH₂ --, --CH₂ CH₂ --S--CH₂ --, --CH═CHCH₂ --O--CH₂ --, --SO₂ NR_(o)--CH₂ -- or --CONH--CH₂ CH₂ --O--CH₂ --, R_(o) hydrogen or an alkylgroup with 1 to 4 carbon atoms, R_(x) is hydrogen or methyl, R_(y) andR_(z) are hydrogen, h is 1, g is 2, and d is zero, and the R_(F) groupis saturated and contains 4-18 carbon atoms, is fully fluorinated andcontains at least one terminal perfluoromethyl group.
 4. A compoundaccording to claim 1, wherein R₁ is a direct bond, --CH₂ --,--CH(CH₃)--, --CH₂ CH₂ --O--CH₂ --, --CH₂ CH₂ --S--CH₂ --, --CH═CHCH₂--O--CH₂ --, --SO₂ NR_(o) --CH₂ -- or --CONH--CH₂ CH₂ --O--CH₂ --, R_(o)is hydrogen or an alkyl group with 1 to 4 carbon atoms, R_(x) ishydrogen or methyl, R_(y) and R_(z) are hydrogen, h and d are 1, g iszero, D is --CH₂ CH₂ --O--CH₂ CH₂ or pentaerythritol diacetate ordipropionate and the R_(F) group is saturated, contains 4-18 carbonatoms, is fully fluorinated and contains at least one terminalperfluoromethyl group.
 5. A compound according to claim 1, wherein R₁ is--CH₂ --, R_(x), R_(z), R_(y) are hydrogen, h is 1, g and d are zero andR_(F) is a fully fluorinated, linear perfluoroalkyl,1 group with 4 to 14carbon atoms.
 6. A compound according to claim 1, wherein the R_(F)group contains a mixture of C₄ F₉ --, C₆ F₁₃ --, C₈ F₁₇ --, C₁₀ F₂₁, C₁₂F₂₅ -- and C₁₄ F₂₉ -- radicals.
 7. A process for the preparation of acompound of the formula I according to claim 1 wherein g is 0, whichcomprises reacting an R_(F) --R₁ --substituted epoxide with Na₂ S, NaHS,elemental sulfur, Na₂ S₄, Na₂ S₅ or an organic dithiol of the formulaHS-D-SH in the presence of water and an organic solvent, where D, R_(F)and R₁ are as defined in claim
 1. 8. A process according to claim 7,wherein said organic solvent is a ketone, ester or alcohol.
 9. A processaccording to claim 8, wherein said organic solvent is selected from thegroup consisting of methyl propyl ketone, methyl ethyl ketone, acetone,ethyl acetate, isopropyl acetate, ethanol, n-propanol, isopropanol, n-,sec.- or tert.-butanol and allyl alcohol.
 10. A process according toclaim 7, wherein said reaction is carried out at a temperature in therange of 40° to 80° C.
 11. A process according to claim 7, wherein saidR_(F) --R₁ substituted epoxide is of the formula R_(F) --EP; R_(F) --CH₂--EP; R_(F) --CH₁ CH₂ --S--CH₂ --EP; R_(F) --CH₂ CH₂ --O--CH₂ --EP,R_(F) CH═CHCH₂ --O--CH₂ --EP, R_(F) --SO₂ NR_(o) --CH₂ --EP or R_(F)--CONH--CH₁ CH₁ --O--CH₁ --EP, where EP denotes an epoxy group and R_(o)is hydrogen or an alkyl group with 1 to 4 carbon atoms.
 12. A processfor the preparation of a compound of the formula I according to claim 1wherein g is 0 and h is 1, which comprises reacting a compound of theformula

    R.sub.F --CHR.sub.v --CR.sub.x (hal)CR.sub.y R.sub.z --OH

with Na₂ S, NaHS, elemental sulfur, Na₂ S₄, Na₂ S₅ or an organic dithiolof the formula HS-D-SH, where hal is bromide or iodide, R_(v) ishydrogen or an alkyl group with 1-5 carbon atoms and R_(F), R_(x), R_(y)and R_(z) are as defined in claim
 1. 13. A process according to claim12, wherein R_(v) and R_(x) are hydrogen or methyl, R_(y) and R_(z) arehydrogen and hal is iodine.